Aryl triflate compound, radiologically acid producing agent, radiologically acid producing agent system, and radiosensitive composition

ABSTRACT

Aryl triflate compounds can generate a strong acid when exposed to irradiation of radiation and can be used as an acid generator in a radiologically-acid-producing agent system and a radiosensitive composition.

BACKGROUND OF THE INVENTION

The present invention relates to a radiosensitive composition which canbe utilized in coating materials, printing materials, UV ink,photoresists for semiconductors, photoresists for printed circuit board,materials for holography, etc.; and an aryl triflate compound, anphoto-acid-producing (or generating) agent (or photo acid generator) oran photo-acid-producing agent system, which is suitable for saidradiosensitive composition.

Practical use of photochemical cationic polymerization was made possibleby use of a thermally stable onium salt found by J. V. Crivello (J. V.Crivello and J. H. Lam, Macromolecules, vol. 10, p. 1307 (1977), etc.).In the photochemical cationic polymerization, as compared withconventionally used photochemical radical polymerization, thepolymerization is not inhibited by air and the lifetime of an activespecies is longer. Therefore, the photochemical cationic polymerizationis advantageous, for example, in that living polymerization is possibleand monomers can be selected in a wide range. Accordingly, earneststudies are in progress in this field. Recent results of investigationon the photochemical cationic polymerization are reviewed in detail inUV Curing: Science and Technology, vol. 1 (1978) and vol. 2 (1984),Technology Marketing Corporation, Norwalk, Conn. A so-called chemicalamplified photoresist has been proposed by a group belonging toInternational Business Machines Corp. The chemical amplified photoresistis highly pervious to excimer laser and has high sensitivity andresolution. Therefore, it is noted as a photoresist for microfabricationof a semiconductor (M. J. Bowden and S. R. Turner, "Polymers for HighTechnology Electronics and Photonics," ACS Symposium Series, U.S.Chemical Society, Washington, D.C. (1987) p. 138, etc.).

Both photochemical cationic polymerization system and chemicalamplification system comprise as their essential constituent a compoundor a system, which produces a strong acid on light irradiation. In thecase of heretofore known onium salts such as triaryl sulfonium salts anddiaryl iodonium salts, the quantum yield of acid production isrelatively high and the strength of an acid produced is sufficient, butthe onium salts are disadvantageous, for example, in that a light sourceis limited because wavelengths at which they are photosensitive areshort, that they have a bad compatibility with generally used resinsystems, that they contain metals, resulting in doping unnecessary inthe semiconductor field, and that soft errors due to radioscopes takeplace. Efforts have been made in various fields to overcome thesedisadvantages. For example, S. P. Pappas, i.e., one of the presentinvestigators, and his co-workers found that the onium salts arephotochemically sensitized by anthracene and the like, wherebyapplication of the onium salts in the near ultarviolet range was madepossible (S. P. Pappas, Journal of Polymer Science, Polymer ChemistryEdition, vol. 22, p. 77-84 (1984). There was attempted a method in whichthe onium salts were improved in compatibility with resin systems byintroducing an alkyl group into the aryl group. In the process disclosedin Japanese Patent Unexamined Publication No. 63-272977, application ofthe onium salts in the semiconductor field is made possible byconverting them into onium salts which contain a counter ion but not ametal.

Acid-producing agents other than the onium salts have also beeninvestigated. For example, there have been disclosed cases in whichthere are used o-nitrobenzyl tosylate (L. F. Thompson, E. Reichmanis, F.M. Houlikan and R. G. Tarascon, Proceedings of the ACS DivisionPolymeric Materials: Science and Engineering, vol. 60, p. 137 (1989)),trichloromethyl-s-triazine (Japanese Patent Unexamined Publication Nos.61-169835 and 61-169837), and a sulfonyl compound (Japanese PatentUnexamined Publication No. 61-166544). However, when theseacid-producing agents are used, the strength of acids produced is notsufficient. There are also known mixed ligand arene cyclopentadienyl Fe(II) salts (J. Lohse and H. Zweifel, Advances in Polymer Science, vol.78, p. 61 (1986)), but they are not free from the defects describedabove, namely, they contain a metal and are ionic. Thus, there is notknown a radiologically-acid-producing agent which can be subjected tospectral sensitization for impartment of sensitivity to a generally usedradiation source, contains neither ionic bond nor metal atom, has asufficiently high efficiency of acid production by radiationirradiation, gives an acid having a high strength, and has a highstorage stability.

SUMMARY OF THE INVENTION

The present invention relates to a radiologically-acid-producing agentor a radiologically-acid-producing system, which have these requiredcharacteristics, an aryl triflate compound capable of giving said agentor system, and a photosensitive composition using said agent or system.

The present invention provides an aryl triflate compound of the generalformula (I) or (II): ##STR1## wherein X is an alkoxycarbonyl group, acyano group, a nitro group or a trifluoromethyl group; Y is a hydrogenatom, a halogen atom, a linear or branched alkyl group, an aralkylgroup, or a substituted or unsubstituted phenyl group; l is an integerof 1 to 5; m is an integer of 1 to 5; and n is zero or an integer of 1to 4, l, m and n being chosen so that l+m+n=6, ##STR2## wherein R is alinear or branched alkyl group having 1 to 22 carbon atoms, an aralkylgroup having 7 to 22 carbon atoms, or a substituted or unsubstitutedphenyl group; Z is a hydrogen atom, a halogen atom or an alkyl group; qis an integer of 1 to 4; and p is zero or an integer of 1 to 3, p and qbeing chosen so that p+q=4.

The present invention also provides an aryl triflate compound of thegeneral formula: ##STR3## wherein R¹ and R² are independently a linearor branched alkyl group having 1 to 22 carbon atoms, an aralkyl grouphaving 7 to 22 carbon atoms, or a substituted or unsubstituted phenylgroup.

The present invention further provides an aryl triflate compound of thegeneral formula: ##STR4## wherein R is a linear or branched alkyl grouphaving 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbonatoms, or a substituted or unsubstituted phenyl group.

The present invention still further provides aradiologically-acid-producing agent comprising any one of the aryltriflate compounds of the formulae (I) to (IV).

The present invention still provides a radiologically-acid-producingagent system comprising any one of the aryl triflate compounds of theformulae (I) to (IV), and at least one sensitizer.

The present invention also provides a radiosensitive compositioncomprising any one of the aryl triflate compounds of the formulae (I) to(IV), and a compound which reacts in the presence of an acid.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are infrared absorption spectra of DMPhTf and NBITf,respectively.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The aryl triflate compound of the present invention is represented bythe general formula (I) or (II): ##STR5## wherein X is an alkoxycarbonylgroup, a cyano group, a nitro group or a trifluoromethyl group; Y is ahydrogen atom, a halogen atom, a linear or branched alkyl grouppreferably having 1 to 22 carbon atoms, an aralkyl group preferablyhaving 7 to 22 carbon atoms, or a substituted or unsubstituted phenylgroup wherein the number of substituent is preferably 1 to 5 and thesubstituents are independently preferably a halogen atom, a cyano group,a straight or branched alkyl group preferably having 1 to 22 carbonatoms, or an alkoxy group preferably having 1 to 20 carbon atoms; l isan integer of 1 to 5; m is an integer of 1 to 5; and n is zero or aninteger of 1 to 4, l, m and n being chosen so that l+m+n=6, ##STR6##wherein R is a linear or branched alkyl group having 1 to 22 carbonatoms, an aralkyl group having 7 to 22 carbon atoms, or a substituted orunsubstituted phenyl group, the substituent being the same as defined inY; Z is a hydrogen atom, a halogen atom or an alkyl group preferablyhaving 1 to 22 carbon atoms; q is an integer of 1 to 4; and p is zero oran integer of 1 to 3, p and q being chosen so that p+q=4.

The present invention further relates to a radiologically-acid-producingagent comprising said compound, and a radiologically-acid-producingagent system and a radiosensitive composition which use said compound.

The aryl triflate compound is preferably an aryl triflate compound ofthe general formula (III): ##STR7## wherein R¹ and R² are independentlya linear or branched alkyl group having 1 to 22 carbon atoms, an aralkylgroup having 7 to 22 carbon atoms, or a substituted or unsubstitutedphenyl group, or an aryl triflate compound of the general formula (IV):##STR8## wherein R is a linear or branched alkyl group having 1 to 22carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or asubstituted or unsubstituted phenyl group.

The novel aryl triflate compound of the present invention containsneither ionic bond nor metal ion and hense can be used for variouspurposes. Trifluoromethanesulfonic acid which said compound produces onradiation irradiation is a superstrong acid, that is, said compoundprovides a sufficiently strong acid.

The aryl triflate of the present invention can be obtained, for example,by condensing 1 equivalent weight of a corresponding phenol: ##STR9##wherein X and Y are as defined above; m is an integer of 1 to 5; and nis zero or an integer of 1 to 4, m and an being chosen so that m+n=5, or##STR10## wherein R and Z are as defined above; and p is zero or aninteger of 1 to 3, with 1.1 equivalent weight oftrifluoromethanesulfonic anhydride (CF₃ SO₂)₂ O in anhydrous pyridine(L. R. Subramanian, M. Hanack, L. W. K. Chang, M. A. Imhoff, P. V. R.Schleye, F. Effenberger, W. Kurtz, P. J. Stang and T. E. Dueber, Journalof Organic Chemistry, vol. 40, p. 4099, (1976)).

Examples of the compound of the formula (I) or (II) are p-nitrophenyltriflate, m-nitrophenyl triflate, o-nitrophenyl triflate,2,4-dinitrophenyl triflate, p-cyanophenyl triflate, m-cyanophenyltriflate, o-cyanophenyl triflate, 3,4-dicyanophenyl triflate,3,4-bis(methoxycarbonyl)phenyl triflate, 3,4-bis(ethoxycarbonyl)phenyltriflate, 3,4-bis(n-propoxycarbonyl)phenyl triflate,3,4-bis(n-butoxycarbonyl)phenyl triflate, 3,4-bis(octoxycarbonyl)phenyltriflate, p-trifluoromethylphenyl triflate, m-trifluoromethylphenyltriflate, o-trifluoromethyl triflate, 4-(N-n-butylphthalimido)-yltriflate, 4-(N-phenylphthalimide)-yl-triflate,4-(N-ethylphthalimido)-yl-triflate,4-[N-(4'-cyanophenyl)phthalimido]-yl-triflate,4-[N-(4'-methylphenyl)phthalimido]-yl-triflate, and4-[N-(4'-bromophenyl)phthalimido]-yl-triflate. These aryl triflatecompounds are useful as radiologically-acid-producing agents which aredecomposed by irradiation with radiation such as X-rays, ultravioletrays, electron beams or the like to produce an acid.

A radiologically-acid-producing agent system obtained by combining anyof these triflates with a suitable sensitizer is sensitive at suitablewavelengths of a radiation source, so that it can have a highsensitivity. Therefore, the combination is desirable. As the sensitizer,known ones can be used in the present invention. Among them,electron-donative sensitizers are preferable. The electron-donativesensitizers include, for example, Micheler's ketone,4,4'-bis(diethylamino)benzophenone, pyrene, anthracene,9-methylanthracene, 9-methoxyanthracene, 9,10-dimethylanthracene,9,10-dimethoxyanthracene, 9-bromoanthracene, 1-methoxyanthracene,2-methoxyanthracene, 1,4-dimethoxyanthracene, perylene, naphthalene,α-methoxynaphthalene, and β-methoxynaphthalene. It is particularlypreferable to use at least one sensitizer selected from anthracene,9-methoxyanthracene and 9,10-dimethoxyanthracene. The ratio of the aryltriflate compound to the sensitizer is usually 1/9 to 10/0 by weight.

The aryl triflate of the present invention or theradiologically-acid-producing agent or agent system obtained bycombining the aryl triflate with at least one sensitizer is made into aradiosensitive composition which produces a reaction product onradiation irradiation, by combining the aryl triflate or the agent oragent system with a compound which reacts in the presence of an acid.

The radiosensitive composition is useful in the above-mentioned coatingmaterials, printing matrices and the like.

As the compound which reacts in the presence of an acid, there are used,for example, compounds having a group which permits cationicpolymerization in the presence of an acid, compounds having a groupwhich permits crosslinking in the presence of an acid, and compoundshaving a bond which is cleaved in the presence of an acid.

As described in Toshinobu Higashimura, "Cationic Polymerization", KozaJugo Hannoron, vol. 3, after p. 3, Kagaku Dojin (1971), the compoundshaving a group which permits cationic polymerization in the presence ofan acid include styrene, vinyltoluene, N-vinylcarbazole,N-vinylpyrrolidone, various vinyl ethers, various vinylidene compounds,vinylene compounds (e.g. 2-methyl-2-butene), conjugated dienes (e.g.1,3-butadiene), cyclic unsaturated compounds (e.g. indene andcyclopentadiene), acetylene compounds (e.g. phenylacetylene), aldehydes,isonitriles, oxirane compounds, tetrahydrafuran compounds, oxetanecompounds, trioxane compounds, β-propiolactone compounds, aziridinecompounds, etc. Various epoxy monomers or prepolymers which areindustrially easily available are also preferably used. They include,for example, various epoxy resins derived from bisphenol A andepichlorohydrin (e.g. Epikote 828, a trade name, Shell Chemical Co.),3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (AralditeCY179, a trade name, Ciba-Geigy Co.), diglycidyl hexahydrophthalate(Araldite CY184, a trade name, Ciba-Geigy Co.), diglycidyl1,2,3,6-tetrahydrophthalate (Araldite CY192, a trade name, Ciba-GeigyCo.), N,N,N',N'-tetraglycidyl-m-xylenediamine (TETRAD-X, a trade name,mfd. by Mitsubishi Gas Chemical Co. Inc.),1,3-bis(N,N-diglycidylaminomethyl)cyclohexyne (TETRAD-C, a trade name,Mitsubishi Gas Chemical Co. Inc.), and various epoxy resins derived fromcresol (or phenol) novolac resins and epichlorohydrin (e.g. EOCN series,trade names, Nippon Kayaku Co., Ltd.). There are also preferably usedhomopolymers obtained by polymerizing an acrylic monomer having an epoxygroup, such as glycidyl acrylate or glycidyl methacrylate, or copolymersobtained by using such a monomer as a comonomer.

The compounds having a group which permits crosslinking in the presenceof an acid include, for example, melamine resins such ashexamethoxymethylolmelamine and the like.

The compounds having a bond which is cleaved in the presence of an acidinclude, for example, poly(α-acetoxystyrenes); polydialdehydes;polyesters, polyethers, polycarbonates and polyacetals which areobtained by using as diol component, 1,4-(2-cyclohexenylene)diol,1,4-dimethyl-2-butine-1,4-diol, 1,4-cyclohexanedial,1,4-dimethylbutane-1,4-diol, 1,1,4,4-tetramethylbutane 1,4-diol,p-xylylenediol, bisphenol A, etc.; and derivatives ofpoly(p-hydroxystyrene) which are obtained by use of t-butyl ether,t-butyl carbonate, tetarhydropyranyl ether, etc.

The radiosensitive composition of the present invention is changed insolubility in a developer by radiation irradiation and hence can be usedas a positive type or negative type resist composition, depending on thekinds of the compound which reacts in the presence of an acid, and thedeveloper. The propotion of the acid-producing-agent or theacid-producing agent system is usually 0.05 to 10% by weight based onthe weight of the radiosensitive composition.

If necessary, the radiosensitive composition of the present inventionmay contain high-molecular-weight polymers such as acrylic resins,polystyrenes, polyesters, polyamides, polyolefin sulfones, cresolresins, phenolic resins, etc.

In addition, the radiosensitive composition of the present invention maycontain additives such as leveling agents, which are known to the art.

In the radiosensitive composition, the using amounts of the aryltriflate compound and the compound which reacts in the presence of anacid are not critical and chosen depending on the change of polarity andmolecular weight of the radiosensitive composition which is caused byradiation irradiation.

The action of the present invention is brought about as follows. Thearyl triflate compound absorbs radiation and then undergoes transitionto a high-energy state, and its Ar-OTf (=-SO₂ CF₃) bond is cleaved togive triflate anion (TfOe), which becomes trifluoromethanesulfonic acid.When an electron-donative sensitizer is combined with the aryl triflatecompound, aryl triflate radical anions produced by the transfer ofelectrons from the sensitizer which has absorbed radiation to fall intoa high-energy state are decomposed to give triflate anions, wherebytrifluoromethanesulfonic acid is produced.

The present invention is illustrated by way of the following Examples.

EXAMPLE 1 a) Synthesis of 4-hydroxy-N-n-butylphthalimide

In a 250-ml round bottom flask were placed 20.5 g (112.6 mmols) of4-hydroxyphthalic acid, 8.2 g (112.6 mmols) of n-butylamine and 100 mlof absolute ethanol. After mixing, the resulting mixture generated heatgently. The mixture was sufficiently stirred until the solids werecompletely dissolved. The alcohol was distilled off under reducedpressure, after which the viscous liquid thus obtained was heated at180° C. for about 3 hours with continuous extraction of water. Aftercooling, the residue was solidified. The solidified residue wasdissolved in an ethyl acetatebenzene (1:1 by volume) mixed solvent, andthe resulting solution was washed with water, an aqueous sodiumcarbonate solution and then water. The organic layer was dried overanhydrous magnesium sulfate, concentrated, and then cooled to obtainpowder crystals having a slightly yellowish white color. The crystalswere collected by suction filtration and dried. Yield: 18.5 g (75%),m.p. 126°-127° C. The product was determined to be4-hydroxy-N-n-butylphthalimide by investigation of its structure by NMRand infrared absorption spectrum.

¹ H NMR (CDCl₃): δ(ppm)=0.80-1.83 (m, 7H, butyl), 3.61 (t, 2H,--N--CH2--, J=6.9 Hz), 7.09 (dd, 1H, 6--ArH, J₅₆ =8.1 Hz, J₃₆ =2.5 Hz),7.25 (d, 1H, 3--ArH, J₃₆ =2.5 Hz), 7.63 (d, 1 H, 5--ArH, J₅₆ =8.1 Hz).

b) Synthesis of 4-(N-n-butylphthalimido)yl triflate (NBITf)

In a 100-ml round bottom flask were placed 3.75 g (17 mmols) of4-hydroxy-N-n-butylphthalimide and 30 ml of anhydrous pyridine (dried onCaH), and cooled with ice water, and 5.15 g (18 mmols) oftrifluoromethanesulfonic anhydride was added dropwise over a period byabout 2 hours with stirring by means of a magnetic stirrer. The stirringwas continued at 0° C. for another 1 hour after completion of thedropwise addition. The reaction mixture was sealed in a container andallowed to stand overnight in a refrigerator (about 5° C). It was thenpoured into ice water, and the solid thus precipitated was collected byfiltration. The solid was dissolved in benzene, and the resultingsolution was washed with water, a 3 wt % aqueous NaOH solution, and thenwater. The organic layer was dried, concentrated, and then cooled toobtain white powder. The powder was collected by suction filtration anddried to find that the yield was 4.08 g (12.1 mmols, 70.8%).

m.p. 68°-69° C.,

¹ H NMR (CDCl₃): δ(ppm)=0.78-1.85 (m, 7H, butyl), 3.67 (t, 2H, N--CH₂--, J=6.6 Hz), 7.54 (dd. 1H, 6--ArH, J₃₆ =2.0 Hz, J₅₆ =7.8 Hz), 7.69 (d,1H, 3--ArH, J₃₆ =2.0 Hz), 7.89 (d, 1H, 5--ArH, J₅₆ =7.8 Hz).

From these results, the compound obtained was confirmed to be NBITf.

EXAMPLE 2 Synthesis of 3,4-bis(methoxycarbonyl)phenyl triflate (DMPhTf)

The title compound was synthesized in the same manner as for NBITfexcept for using dimethyl 4-hydroxyphthalate in place of4-hydroxy-N-n-butylphthalimide. Thus, a colorless liquid was obtained.

¹ H NMR (CDCl₃): δ(ppm)=3.91 (s, 3 H, ester), 3.92 (s, 3 H, ester), 7.45(dd, 1 H, 6--ArH, J₂₅ =2.4 Hz, J₅₆ =8.4 Hz), 7.68 (d, 1 H, 3--ArH, J₂₅=2.4 Hz), 7.82 (d, 1H, 5--ArH, J₅₆ =8.4 Hz).

From these results, the compound obtained was confirmed to be DMPhTf.

EXAMPLE 3 Synthesis of 4-(N-phenylphthalimide)-yl-triflate (NPhITf)

4-Hydroxy-N-phenylphthalimide was synthesized from 4-hydroxyphthalicacid and aniline in the same manner as in Example 1, a). By the reactionof the synthesized compound with trifluoromethanesulfonic anhydride,4-(N-phenylphthalimide)-yl-triflate (NPhITf) was synthesized.

m.p. 116.5°-117.5° C.

¹ H NMR (CDCl₃): δ(ppm)=7.28-7.53 (m, 5 H, N-phenyl), 7.68 (dd, 1 H,6--ArH, J₃₆ =2.0 Hz, J₅₆ =8.1 Hz), 7.84 (d, 1 H, 3--ArH, J₃₆ =2.0 Hz),8.03 (d, 1 H, 5--ArH, J₅₆ =8.1 Hz).

Infrared absorption spectra of NBITf and DMPhTf are shown in FIG. 1 andFIG. 2, respectively.

EXAMPLES 4 TO 7

Production of an acid by light irradiation was investigated by use ofthese aryl triflates. Solutions were prepared by using methylenechloride as solvent and each of the combinations shown in Table 1 of thearyl triflate (DMPhTf or NBITf) and a sensitizer selected fromanthracene (An), 9-methoxyanthracene (9-MoA) and9,10-dimethoxyanthracene (9,10-DMoA). Each solution was irradiated withmonochromatic light having a wavelength of 365 nm and the acid thusproduced was quantitatively determined. The monochromatic light having awavelength of 365 nm was obtained by using a 450 W moderate pressuremercury arc lamp (Hanovia, Model 679-A36, mfd. by American Ace Co.) aslight source and a 7-83 combination filter mfd. by Corning Glass Works.The light irradiation was carried out by use of a merry-go-round typephotoreaction apparatus. The quantitative determination of the acid wascarried out by the dye bleaching method by Gaines (G. E. L. Gaines,Analytical Chemistry, vol. 48, No. 2, p. 450 (1976)). The resultsobtained are shown in Table 1. The concentration of the aryl triflatewas adjusted to 10⁻² M (mol/liter) and that of the sensitizer to eachvalue shown in Table 1, whereby the absorbance was adjusted to 2.0 to2.6.

                                      TABLE 1                                     __________________________________________________________________________    Optical acid production by aryl triflate                                                  Example                                                                       4      5      6      7                                            __________________________________________________________________________    Aryl triflate                                                                             DMPhTf DMPhTf DMPhTf NBITf                                        Sensitizer  An     9-MoA  9,10-DMoA                                                                            9-MoA                                        (sensitizer concentration,                                                                (9.46 × 10.sup.-4)                                                             (3.18 × 10.sup.-4)                                                             (3.69 × 10.sup.-4)                                                             (3.18 × 10.sup.-4)                     mol/liter)                                                                    Quantum yield of                                                                          2.16 × 10.sup.-3                                                               1.86 × 10.sup.-3                                                               3.03 × 10.sup.-3                                                               1.08 × 10.sup.-3                       acid production                                                               __________________________________________________________________________

The aryl triflate compound of the present invention produces asuperstrong acid efficiently on radiation irradiation and hence issuitable as a material for a radiologically-acid-producing agent or aradiologically-acid-producing agent system. A radio-sensitivecomposition comprising said aryl triflate compound can be used inphotochemically cationic-polymerizable compositions and chemicalamplification type resists and exhibit desirable characterics.

What is claimed is:
 1. A radiologically-acid-producing agent systemcomprising an aryl triflate compound and at least one sensitizer, saidaryl triflate compound being selected from the group consisting of anaryl triflate compound of the formula: ##STR11## wherein X is analkoxycarbonyl group, a cyano group, a nitro group or a trifluoromethylgroup; Y is a hydrogen atom, a halogen atom, a linear or branched alkylgroup, an aralkyl group, or a substituted or unsubstituted phenyl group;l is an integer of 1 to 5; m is an integer of 1 to 5; and n is zero oran integer of 1 to 4, l, m and n being chosen so that l+m+n=6,an aryltriflate compound of the formula: ##STR12## wherein R is a linear orbranched alkyl group having 1 to 22 carbon atoms, an aralkyl grouphaving 7 to 22 carbon atoms, or a substituted or unsubstituted phenylgroup; Z is a hydrogen atom, a halogen atom or an alkyl group; q is aninteger of 1 to 4; and p is zero or an integer of 1 to 3, p and q beingchosen so that p+q=4, an aryl triflate compound of the formula:##STR13## wherein R¹ and R² are independently a linear or branched alkylgroup having 1 to 22 carbon atoms, an aralkyl group having 7 to 22carbon atoms, or a substituted or unsubstituted phenyl group, and anaryl triflate compound of the formula: ##STR14## wherein R is a linearor branched alkyl group having 1 to 22 carbon atoms, an aralkyl grouphaving 7 to 22 carbon atoms, or a substituted or unsubstituted phenylgroup.
 2. A radiologically-acid-producing agent system according toclaim 1, wherein the sensitizer is an electron-donative sensitizer.
 3. Aradiologically-acid-producing agent system according to claim 1, whereinthe sensitizer is selected from the group consisting of anthracene,9-methoxyanthracene and 9,10-dimethoxyanthracene.
 4. A radiosensitivecomposition comprising an aryl triflate compound and a compound whichreacts in the presence of an acid, said aryl triflate compound beingselected from the group consisting of an aryl triflate compound of theformula: ##STR15## wherein X is an alkoxycarbonyl group, a cyano group,a nitro group or a trifluoromethyl group; Y is a hydrogen atom, ahalogen atom, a linear or branched alkyl group, an aralkyl group, or asubstituted or unsubstituted phenyl group; l is an integer of 1 to 5; mis an integer of 1 to 5; and n is zero or an integer of 1 to 4, l, m andn being chosen so that l+m+n=6,an aryl triflate compound of the formula:##STR16## wherein R is a linear or branched alkyl group having 1 to 22carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or asubstituted or unsubstituted phenyl group; Z is a hydrogen atom, ahalogen atom or an alkyl group; q is an integer of 1 to 4; and p is zeroor an integer of 1 to 3, p and q being chosen so that p+q=4, an aryltriflate compound of the formula: ##STR17## wherein R¹ and R² areindependently a linear or branched alkyl group having 1 to 22 carbonatoms, an aralkyl group having 7 to 22 carbon atoms, or a substituted orunsubstituted phenyl group, and an aryl triflate compound of theformula: ##STR18## wherein R is a linear or branched alkyl group having1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or asubstituted or unsubstituted phenyl group.
 5. A radiosensitivecomposition according to claim 4, wherein the compound which reacts inthe presence of an acid is a compound having a group which undergoescationic polymerization in the presence of the acid.
 6. A radiosensitivecomposition according to claim 4, wherein the compound which reacts inthe presence of an acid is a compound having a group which undergoescrosslinking in the presence of the acid.
 7. A radiosensitivecomposition according to claim 4, wherein the compound which reacts inthe presence of an acid is a compound having a bond which is cleaved inthe presence of the acid.
 8. A radiosensitive composition according toclaim 4, which further comprises a sensitizer.